CRYSTAL STRUCTURES OF [Bu4N]2[M2Ag3（ μ3—S）2（μ—S）4S2Et2dtc]（M=W,Mo）

<正> The title compounds were prepared from the reation of (NH4)2MS4 (M=W,Mo),AgNO3,NadtcEt2 and Et4NBr in CH3CN-H2O solution. The isomorphous compounds [Bu4N]2[W2Ag3S8Et2du] ( I ) and [Bu4N]2[Mo2Ag3S8Et2dtc] (Ⅱ) crystallize in triclinic space qroup Pi with the following crystal parameters:α=13. 043(4),b = 21. 640(6),c=10. 757(6)A ,α=95. 09(5),β = 91. 90(4),γ = 98. 57(3)°,Z = 2,V = 2987A3,Dc=1. 76g/cm3 for I 5;a= 12. 989(2) ,b=21. 574 (9) ,c= 10. 7/1(1) A .α= 95. 06(7), β=91. 61(4), γ=98. 52(2)°, Z = 2,V = 2961 A3.Dc= 1. 58g/cm3 for Ⅱ . The final R and Rw values are 0. 061 and 0. 072 for Ⅰ ,and 0. 062 and 0. 076 for Ⅱ The M2Ag3 (M = W, Mo) unit in anion M2Ag3S8Et2dtc forms a five-membered ring.     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE TRI-(μ2-METHOXY)-BRIDGED 'DOUBLE-CUBANE' CLUSTER COMPLEX (Et_4N)_3[Mo_2Fe_6S_8(OMe)_3(SPh)_6]

<正> The title compound was synthesized and crystal structure was solved. (Et4N)3[Mo2Fe6S8(OMe)3(SPh)6], Mr=1922.39, hexagonal, PGs/m, a = 17.750(3), c=15.880(2) A, V=4332.7(26) A3, Z-2, Dx=1.477 g/cm3, MoKα, λ= 0.71069 A, R = 0.059, Rw = 0.065, for 814 observed reflexions. The complex anion contains two Fe3MoS4 cubane-like units linked throug their molybdenum atoms by three ,μ2-methoxy-groups, and the overall structure of the anion has C3b symmetry.     

钼铁硫原子簇化合物的合成与结构化学研究II: 以Fe(SR)6为桥的双类立方烷化合物的合成及(Et4N)4[Mo2Fe7S8(SC6H4CH3-m)12].2THF的晶体结构

在乙腈溶液中(Et4N)2[Fe4(SR)10]与(Et4N)2[MoS4]反应半小时生成对氧极为敏感的系列黑色晶状化合物(Et4N)4[Mo2Fe7S8(SR)12](R=C6H5,1;R=C6H4CH3-m, 2;R=C6H4CH3-o, 3;R=C6H4CH3-ρ,4). 2.2THF晶体的分子量为2982.8, 属单斜晶系;空间群为P21/n; a=18.022(2), b=18.375(2), c=22.254(3)A; β=71.04(1)°;V=6969(2)A^3;Dc=1.424g.cm^-^3;Z=2;F(000)=3108.晶体结构用直接法解出,修正至R=0.064. 2.2THF中Mo...Mo'距离为7.234A.     

SYNTHESIS AND STRUCTURE OF[Et_4N]_3[FE_3(SPh)_3Br_3Cl_3]

<正> The title compound was synthesized and its structure solved. The formula is [Et4N]3[Fe3(SPh)3Br3Cl3]. M=1231.95, monoclinic, space group C2/c, a=24.569(4), b=13.504(2), c=18.348.(3)A, β=110.78(1)°, V=5691(3)A3, Z=4, Dm= 1.41, Dc=1.44-g/cm3. The flat structure of the anion has. a planar [Fe3S3] ring and three phenyl groups. Statistical distribution of chlorine and bromine atoms on two sides of the [Fe3S3] plane results in a C2 symmetry of the anion.     

SYNTHESIS AND STRUCTURE OF BIS (TETRAETHYLAMMONIUM)-DIPHENYLTHIO LATODITHIOFERRATO-S, S'''' )-DIOXOMOLYBDATE,(Et_4N)_2 [O_2MoS_2Fe (SC_6H_5)_2]

<正> (Et_4N)_2[O_2MoS_2Fe(SPh)_2],M= 726. 77,orthorhombic, space group P212121,with a=12. 434(2),b=10. 162(3),c=28. 285(2) A,V=3573. 8(14) A3,Z = 4,Dc=1. 351gcnr-3,D0=1. 36gcm-3(flotation)λ(MoKa) = 0. 71069A ,μ=10. 0cm-1, F(000) = 1520,T=298K. The structure was solved by heavy-atom method and refined by full-matrix least squares techniques to final R=0. 071 and Rw = 0. 074 for 1992 reflections (I≥3σ(I)). The title complex is a hetero dimetallic cluster containing a planar Mo(μ-S)2Fe rhomboidal core with the Mo-Fe distance of 2. 765(2) A.     

铁铂硫原子簇化合物的合成与结构研究 V: [MoFe3S4]类立方烷簇合物的转化反应和[Et4N]3[Mo2Fe6S8(SC6H4CH3-m)3Cl6]的晶体结构

具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

The Synthesis and Crystallographic Characterization of Heterotrimetallic Linear Complex of [Et_4N][ (Ph_3P)_2{CuS_2WS_2Fe} Br_2]

1INTRoDUCTIONMolybdenum(Tungsten)-copper-sulfurandmolydenum(tungsten)-iron-sulfurcompoundshavebeenstudiedextensivelybecauseoftheirconnectionwithbiologicalprocesses[l,2j.Someheterotrimetalliccomplexeshavebeensynthesized,suchas[NEt'jtPh,p)sAgSzMoSzCu(CN))and[NEt'jtPh,P),AgS,MooCu(CN)jt3i,[l(CH,CH,)'j(PPh,)2{AgS2WS2Cu}(CN)jt4i,[(CH,CH2)4j(PPh,)2{AgS,WOCu}(CN)j('3,butheterotrimetal1iccomplexescontainingtungsten,copper,andironatomshaveseldombeenreported.Onecomplexofthiskindha…     

Heterobimetallic Clusters of Copper(I) with Trithiotungstate and Trithiomolybdate. Synthesis and Characterization of the Octanuclear Clusters [Et(4)N](4)[M(4)Cu(4)S(12)O(4)] (M = Mo, W) and the Dodecanuclear Clusters [M(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (M = Mo, W; TMEN = N,N,N',N'-Tetramethylethylenediamine)

Synthetic methods for [Et(4)N](4)[W(4)Cu(4)S(12)O(4)] (1), [Et(4)N](4)[Mo(4)Cu(4)S(12)O(4)] (2), [W(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (3), and [Mo(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (4) are described. [Et(4)N](2)[MS(4)], [Et(4)N](2)[MS(2)O(2)], Cu(NO(3))(2).3H(2)O, and KBH(4) (or Et(4)NBH(4)) were used as starting materials for the synthesis of 1 and 2. Compounds 3 and 4 were produced by reaction of [Et(4)N](2)[WOS(3)], Cu(NO(3))(2).3H(2)O, and TMEN and by reaction of [Me(4)N](2)[MO(2)O(2)S(8)], Cu(NO(3))(2).3H(2)O, and TMEN, respectively. Crystal structures of compounds 1-4 were determined. Compounds 1 and 2 crystallized in the monoclinic space group C2/c with a = 14.264(5) ?, b = 32.833(8) ?, c = 14.480(3) ?, beta = 118.66(2) degrees, V = 5950.8(5) ?(3), and Z = 4 for 1 and a = 14.288(5) ?, b = 32.937(10) ?, c = 14.490(3) ?, beta = 118.75(2) degrees, V = 5978.4(7) ?(3), and Z = 4 for 2. Compounds 3 and 4 crystallized in the trigonal space group P3(2)21 with a = 13.836(6) ?, c = 29.81(1) ?, V = 4942(4) ?(3), and Z = 3 for 3 and a = 13.756(9) ?, c = 29.80(2) ?, V = 4885(6) ?(3), and Z = 3 for 4. The cluster cores have approximate C(2v) symmetry. The anions of 1 and 2 may be viewed as consisting of two butterfly-type [CuMOS(3)Cu] fragments bridged by two [MOS(3)](2-) groups. Eight metal atoms in the anions are arranged in an approximate square configuration, with a Cu(4)M(4)S(12) ring structure. Compounds 3 and 4 can be considered to consist of one [M(4)Cu(4)S(12)O(4)](4-) (the anions of 1 and 2) unit capped by Cu(TMEN)(+) groups on each M atom; the Cu(TMEN)(+) groups extend alternately up and down around the Cu(4)M(4) square. The electronic spectra of the compounds are dominated by the internal transitions of the [MOS(3)](2-) moiety. (95)Mo NMR spectral data are investigated and compared with those of other compounds.     

REACTIVITY OF METAL(O) DITHIOCARBAMATO CARBONYL COMPLEXES [Mo(CO)_4(S_2CNEt_2)]~- (M=Mo, W): SYNTHESIS AND STRUCTURE OF A NEW MIXED-VALENCE DINUCLEAR MOLYBDENUM-SULFUR COMPLEX, [Et_4N]_2[(CO)_4MoS_2MoS_2]

<正> The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.     

SYNTHESIS AND STRUCTURE OF A NEW LINEAR TETRANUCLEAR Mo-Fe-S CLUSTER (Et_4N)_2[(Et_2NCSSMoS_2)_2O_3Fe_2S_2]·DMF

<正> (Et4N)2[Et2NCSSMoS2)2O3Fe2S2]·DMF(1) ,Mr= 1174. 10,mono-clinic,space group P21/n,a = 9. 608(3),b=17. 962(2),c=15. 312(3) A ,β=95. 03 (3)°,V=2632. 4 A3,Dc= 1. 48 g/cm3 and Z=2. The structure was solved from 2499 reflections with I>3σ(Ⅰ) and refined by full-matrix least squares method to R(Rw) = 0. 073(0. 087). The anion of 1 has linear Mo -Fe -Fe-Mo array. The oxidation states of metal atoms in this cluster are 2Mo(Ⅵ) + 2Fe(Ⅲ).     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound [Et4N ] 2 [Mo2 (CO) 8 (SC6H4-OCH3-p) 2]

Reaction of Mo(CO)6 with p-H3CO-C6H4SNa and Et4NCl · H2O in CH3CN afforded a dinuclear molybdenum(0) compound [Et4N]2[Mo2 (CO)8 (SC6H4-OCH3-p)2] (1). The crystal structure was determined by X-ray diffraction. The crystallographic data: C38H54Mo2N2O10S2, Mr = 954.87, triclinic, P-1, a = 11.348 (7), b =11.616(5), c=10.065(7) A, a=113.86(4), β=111.39(5), γ=91.92(5)°, V=1104.0(1) A3, Z=1, Dc=1.44 g/cm3, F(000)=492, μ=7.0cm-1, Final R=0. 046 and Rw=0. 049 for 2657 reflections with I＞3. Oσ(I). The X-ray structure analysis revealed that the Mo2S2 core of 1 is planar. The geometry around each Mo atom is a distorted octahedron, the two octahedrons form an edge-sharing bioctahedron. The bond. In addition, the 95Mo NMR chemical shift of 1 is discussed.     

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

MoFe_3S_4单立方烷自兜合成及(Et_4 N)(MoFe_3S(Et_2dtc)_5]·MeCN的晶体结构

<正> 具有MoFe_3S_4单立方烷簇骼的化合物与固氮酶的钼铁蛋白及铁钼辅基存在着某些类似性,从而引起人们的极大注意。1973年卢嘉锡提出的固氮酶活性中心模型—福州模型(Ⅰ)—就具有网兜状缺口MoFe_3S_3单立方烷结构。迄今,还没有见到用简单化合物一步合成,即所谓自兜(Spontaneous self-assembly)合成单立方烷的报导。     

Synthesis and structure of the organometallic MFe2(mu3-S)2 clusters (M = Mo or Fe)

New organometallic clusters with the MFe2(mu3-S)2 core (M = Mo or Fe) have been synthesized from inorganic [MoFe3S4] or [Fe4S4] clusters under high pressure CO. The reaction of (Cl4-cat)2Mo2Fe6S8(PR3)6[R = Et, (n)Pr] with high pressure CO produced the crystalline [MoFe2S2]4+ clusters, (Cl4-cat)Mo(O)Fe2S2(CO)(n)(PR3)6-n[n= 4, Et =I, (n)Pr =II; n = 5, Et =III] after flash column chromatography. The similar [MoFe2S2]4+ cluster, (Cl4-cat)2MoFe2S2(CO)2(depe)(2)(IV), also has been achieved by the reactions of (Cl4-cat)MoFe3S3(CO)6(PEt3)2 with depe by reductive decoupling of the cluster. For the [Fe3(mu3-S)2]4+ cluster, [Fe4S4(PcHex3)4](BPh4) was reacted with high pressure CO to produce a new Fe3S2(CO)7(PcHex)(2)(V) compound. These reactions generalized the preparation of organometallic compounds from inorganic clusters. All the compounds have been characterized by single crystal X-ray crystallography. A possible reaction pathway for the synthesis of the MFe2(mu3-S) clusters (M = Mo or Fe) has also been suggested.     

Magnetic Properties of Phenoxy－Bridged Binuclear Iron－Thiolato Complexes and Structure of （Et_4N）_2［Fe_2（o－OC_6H_4S）_2（o－OC_6H_4SH）_2］

ＭａｇｎｅｔｉｃＰｒｏｐｅｒｔｉｅｓｏｆＰｈｅｎｏｘｙ－ＢｒｉｄｇｅｄＢｉｎｕｃｌｅａｒＩｒｏｎ－ＴｈｉｏｌａｔｏＣｏｍｐｌｅｘｅｓａｎｄＳｔｒｕｃｔｕｒｅｏｆ（Ｅｔ_４Ｎ）_２［Ｆｅ_２（ｏ－ＯＣ_６Ｈ_４Ｓ）_２（ｏ－ＯＣ_６Ｈ_４ＳＨ）_２］ＸＩＥＸｉ?..     

Synthesis and Structural Characterization of a Salt{[Co(Phen)3][Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O)(Phen = 1,10-Phenanthroline,edt = Ethane-1,2-dithiolate)

Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2(6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) (A), β = 92.835°, V = 9829.3(3) (A)3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co-N and Mo…Mo bond distances are 2.139 and 2.872 (A), respectively.     

SYNTHESES AND CRYSTAL STRUCTURE OF [Et_4N]{Mo(CO)_5L}(L=I~-,SPh~-)

<正> Crystal of [Et4N][Mo(CO)5I](1) (Mr = 493. 15) is tetragonal with space group P4/n, a =b==9. 374(2) ,c=10. 545(2)(?), V=926. 5(?)3, Z = 2, F(000) = 480, Dc=1. 77g/cm3and μ = 23. 6cm-1. R = 0. 040, Rw = 0.043 for 374 observed reflections. Crystal of [Et4N][Mb(CO)5(SPh)] (2) is orthorhombic ith space group Pbam, a= 15. 230(3), b = 18. 389(10), c=8. 172(3)(?), V=2288. 6 (?)3, Z = 4, Dc=1. 38gcm3, μ = 6.7cm-1.R = 0. 043, Rw = 0. 042 for 1621 observed reflections. Complexes 1 and 2 possess the same geometry. The Mo atom is octahe-drally coordinated with obvious trans drrdct, all the Mo -C bond lengths are shorter obviously and the C - O bond are longer than those of Mo(CO)6.